CN86107795A - The triazole compounds of coordinate plant growth - Google Patents
The triazole compounds of coordinate plant growth Download PDFInfo
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- CN86107795A CN86107795A CN198686107795A CN86107795A CN86107795A CN 86107795 A CN86107795 A CN 86107795A CN 198686107795 A CN198686107795 A CN 198686107795A CN 86107795 A CN86107795 A CN 86107795A CN 86107795 A CN86107795 A CN 86107795A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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Abstract
The invention relates to the triazole compounds of coordinate plant growth, its molecular formula is
X in the formula, Ar, R
1, R
2And R
3As definition in the specification sheets.
Description
The worker in agrochemistry and plant physiology field know some pharmaceutical chemicalss effectively controlling plant behavior for some time.Some compounds that for example obtained can change the growth of plant, increase crop yield, improve the quality of farm crop or improve mechanical harvesting by changing the plant-growth habit.Be applied to plant and be called plant-growth regulator with the physiological process of change effectively and the compound of structure.The growth that slows down turf with the cane that reduces the frequency of mowing, shorten cereal grass with the lodging that reduces plant, impel ornamental plant to grow compactly more, increase and fructovegetatively bloom, increase tomato strain shape solid, that dwindle cereal grass and enable dense planting, these all are some examples of coordinate plant growth purpose.
The molecular formula of triazole compounds provided by the invention is
In the formula
X:-O-or-S-;
Ar: phenyl or be selected from halogen, trifluoromethyl, C arbitrarily by 1 or 2
1-C
3Alkyl, C
1-C
3Alkoxyl group, difluoro-methoxy, trifluoromethoxy, five fluorine oxyethyl groups and 1,1,2, the group substituted-phenyl of 2-tetrafluoro ethoxy;
R
1: C
1-C
4Primary alkyl or secondary alkyl;
R
2: hydroxyl, C
1-C
4Alkoxyl group, benzyloxy, phenoxy group or-NR
4R
5;
R
3: hydrogen or C
1-C
4Primary alkyl or secondary alkyl;
R
4And R
5: hydrogen, C arbitrarily
3-C
6Cycloalkyl or C
1-C
3Alkyl, or R
4And R
5Interosculate generation morpholino, tetramethyleneimine for (pyrrolidino) or piperidino-(1-position only) with nitrogen-atoms; Or its salt that can be accepted by plant;
The present invention also provides the agricultural that comprises above-claimed cpd and the receptible thinner of plant with medicine with the method for coordinate plant growth further is provided, and comprises that significant quantity with the compound of above-mentioned molecular formula is used to regulate the plant before the later stage generative growth phase.
All temperature are all used and degree centigrade are represented that all concentration, ratio etc. are all used weight unit except other marks herein.
In the above-mentioned molecular formula, the general technical term of chemistry all are the connotation of using always, for example C
1-C
3Alkyl and C
1-C
3Alkoxyl group then is to comprise methyl, ethyl, propyl group, sec.-propyl, and they can be connected to form the alcoxyl base class by Sauerstoffatom.C
1-C
4Alkoxyl group comprises above-mentioned alcoxyl base class, also comprises butoxy, 1-methyl propoxy-, 2-methyl propoxy-and tert.-butoxy.C
1-C
4Primary alkyl or secondary alkyl comprise methyl, ethyl, propyl group, sec.-propyl, butyl, 1-methyl-propyl and 2-methyl-propyl.C
3-C
6Cycloalkyl comprises some groups as cyclopropyl, cyclobutyl and cyclohexyl.
Halogen comprises fluorine, chlorine, bromine and iodine (base).
Above-mentioned molecular formula has been introduced compound of the present invention, but the following compound group of mentioning is especially be sure of to be easier to understand the present invention.
3-(1-carboxyl oxyethyl group)-and the 1-(2-fluorophenyl)-1,2, the 4-1H-triazole
3-(1-carboxyl propoxy-)-and the 1-(4-chloro-phenyl-)-1,2,4-1H-triazole, sodium salt
The 1-(3-bromophenyl)-3-(1-methoxycarbonyl butylthio)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
3-(1-ethoxycarbonyl-2-methyl propoxy-)-and the 1-(4-iodophenyl)-1,2, the 4-1H-triazole
5-ethyl-3-(1-propoxycarbonyl penta sulfenyl)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
3-(1-isopropoxy carbonyl-2-methyl butoxy)-and 5-methyl isophthalic acid-(3-aminomethyl phenyl)-1,2, the 4-1H-triazole
3-(1-butoxy carbonyl-3-methyl butoxy)-the 1-(2-ethylphenyl)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
3-(1-isobutoxy carbonyl oxyethyl group)-and 5-sec.-propyl-1-(4-isopropyl phenyl)-1,2, the 4-1H-triazole
3-(1-s-butoxy carbonyl oxyethyl group)-the 1-(4-p-methoxy-phenyl)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
3-(1-t-butoxy carbonyl propoxy-)-the 1-(3-ethoxyl phenenyl)-5-phenyl-1,2, the 4-1H-triazole
3-(1-benzyloxycarbonyl oxyethyl group)-the 1-(2-isopropyl phenyl)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
5-butyl-3-(1-carboxyl ethylmercapto group)-and 1-(3, the 5-difluorophenyl)-1,2,4-1H-triazole, sylvite
1-(2, the 4-dibromo phenyl)-5-methyl-3-(1-phenyloxycarbonyl butoxy)-1,2, the 4-1H-triazole
3-(1-aminocarboxyl oxyethyl group)-and 1-(3, two (trifluoromethyl) phenyl of 5-)-1,2, the 4-1H-triazole
3-(1-methylamino carbonyl oxyethyl group)-and 1-(2, the 5-3,5-dimethylphenyl)-1,2, the 4-1H-triazole
3-(1-ethylamino-carbonyl ethylmercapto group)-and 1(2, the 6-3,5-dimethylphenyl)-1,2, the 4-1H-triazole
The 5-(1-aminomethyl phenyl)-and 1-(3, two (methoxyl group) phenyl of 4-)-3-(1-Propylamino carbonyl propoxy-)-1,2, the 4-1H-triazole
3-(1-isopropylamine base carbonyl oxyethyl group)-and 1-(2, two (propoxy-) phenyl of 4-)-1,2, the 4-1H-triazole
3-(1-ethyl dimethylamine base carbonyl-2-methyl propoxy-)-and 1-(2-fluoro-4-trifluoromethyl)-1,2, the 4-1H-triazole
1-(3-bromo-5-chloro-phenyl-)-and 5-isobutyl--3-(1-hexichol amido hydroxyl-oxethyl)-1,2, the 4-1H-triazole
3-(1-ethylbenzene amido carbonyl ethylmercapto group)-and 1-(4-fluoro-3-iodophenyl)-1,2, the 4-1H-triazole
1-(3-chloro-4-ethylphenyl)-the 3-(1-sec.-propyl adds amido carbonyl pentyloxy)-1,2, the 4-1H-triazole
1-(2-bromo-4-isopropyl phenyl)-and 3-(1-morpholino carbonyl oxyethyl group)-1,2, the 4-1H-triazole
1-(2-fluoro-5-aminomethyl phenyl)-the 3-(1-tetramethyleneimine is for the carbonyl oxyethyl group)-1,2, the 4-1H-triazole
1-(2-chloro-3-p-methoxy-phenyl)-and 5-methyl-3-(1-piperidino-(1-position only) carbonyl-2-methyl butylthio)-1,2, the 4-1H-triazole
3-(1-carboxyl oxyethyl group)-and 1-(2-fluoro-4-isopropyl phenyl)-1,2, the 4-1H-triazole
3-(1-methoxycarbonyl oxyethyl group)-and 1-(4-methyl-3-trifluoromethyl)-1,2, the 4-1H-triazole
3-(1-carboxyl oxyethyl group)-and 1-(2-propyl group-4-trifluoromethyl)-1,2,4-1H-triazole, triethylamine salt
1-(3-oxyethyl group-5-trifluoromethyl)-and 3-(1-propoxycarbonyl-3-methyl butylthio)-1,2, the 4-1H-triazole
3-(1-aminocarboxyl oxyethyl group)-and 1-(4-isopropoxy-2-trifluoromethyl)-1,2, the 4-1H-triazole
1-(4-methoxyl group-3-aminomethyl phenyl)-and 5-methyl-3-(1-phenyloxycarbonyl ethylmercapto group)-1,2, the 4-1H-triazole
3-(1-carboxyl propoxy-)-and 1-(5-oxyethyl group-2-propyl group phenyl)-1,2,4-1H-triazole, pyridinium salt
3-(1-carboxyl oxyethyl group)-and 1-(4-isopropoxy-2-isopropyl phenyl)-1,2, the 4-1H-triazole
The 1-(4-chloro-phenyl-)-and 3-(1-cyclopropyl amino carbonyl rosickyite base)-1,2, the 4-1H-triazole
3-(1-(cyclobutyl) (first) amido carbonyl ethylmercapto group)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
3-(1-cyclohexylamino carbonyl oxyethyl group)-and 1-(3, the 5-dichlorophenyl)-1,2, the 4-1H-triazole
3-(1-(cyclopentyl) (second) amido carbonyl-2-methyl propoxy-)-and 5-methyl isophthalic acid-(3, the 5-3,5-dimethylphenyl)-1,2, the 4-1H-triazole
3-(two (ring fourth) the amido carbonyl ethylmercapto groups of 1-)-1-phenyl-1,2, the 4-1H-triazole
1-(4-chloro-3-aminomethyl phenyl)-3-(1-cyclopropyl amino carbonyl propoxy-)-5-ethyl-1,2, the 4-1H-triazole
3-(1-cyclohexylamino carbonyl butylthio)-and the 1-(3-p-methoxy-phenyl)-1,2, the 4-1H-triazole
3-(1-carboxyl oxyethyl group)-and 1-(3, the 5-dichlorophenyl)-1,2,4-1H-triazole, triethylamine salt
3-(1-carboxyl oxyethyl group)-and 1-(3, the 5-3,5-dimethylphenyl)-1,2, the 4-1H-triazole
Though all compounds of the present invention all are useful, wherein some substate compound especially can preferentially adopt.
The compound of a best like this class comprises that molecular formula is
In the formula:
Ar: phenyl or be selected from fontanel, trifluoromethyl, C arbitrarily by 1 or 2
1-C
3Alkyl or C
1-C
3The group substituted-phenyl of alkoxyl group;
R
1: C
1-C
4Primary alkyl or secondary alkyl;
R
2: hydroxyl, C
1-C
4Alkoxyl group, benzyloxy, phenoxy group or-N(R
6) (R
7);
R
3: hydrogen, or C
1-C
4Primary alkyl or secondary alkyl;
R
6And R
7: hydrogen or C arbitrarily
1-C
3Alkyl, or R
6And R
7Mutual chemical combination and combine with nitrogen-atoms and to generate morpholino, tetramethyleneimine generation or piperidino-(1-position only); And the salt that can be accepted by plant.
One compounds that can especially preferentially adopt comprises X:O, R
1: methyl, R
2: OH or (C
1-C
4) alkoxyl group, R
3: H, Ar:3-chloro-phenyl-, 4-chloro-phenyl-, or 3, the 4-dichlorophenyl.
Compound of the present invention can be by being similar to the method economy and facility ground preparation of known synthesis step.These methods are generally only done concise and to the point discussion here, and following preparation embodiment will explain the synthetic of these compounds and intermediate thereof.
First intermediate of these compounds is to have substituent 1-N-anilides base urea on the phenyl ring of the required product feature of performance.Urea,amino-is easy to by corresponding phenylhydrazine, preferentially adopts fontanel hydrogenation salt, with hydrochlorate, preferentially adopts the reaction of alkali metal cyanate salt form to obtain.
When adopting optimum response agent form, present method is easy to realize in water under 50～100 ℃ suitable hot conditions.Suitable reaction times such as several hrs are enough to produce best yield.
When needs prepared X for the compound of-S-, intermediate can prepare the 1-phenylthiosemicarbazide by thiocyanate-certainly.
Adopt above-mentioned steps and other following steps, present method can obtain the highest yield or maximum production, may also be best in this case.Certainly, The optimum reaction conditions also will respectively have difference because of required purpose difference.So, will find, in order to obtain the highest yield or maximum production, the very easy realization of synthesis step, and, just need not to use excessive any reagent in order to utilize other reagents well.
Second intermediate of this synthetic is 3-hydroxyl (thion)-1-aryl-1,2, the 4-1H-triazole, and it is obtained by amino (sulphur) urea and ortho ester prepared in reaction.When required product does not have 5-substituting group (R
3: in the time of hydrogen), manthanoate is an ortho-formiate.Formic acid can be used for replacing ortho-formiate.Have the 5-substituting group as product, can select for use manthanoate that required substituting group is provided.For example, provide 5-methyl product with ortho-acetate; Provide 5-propyl group product with former butyric ester.
When the manthanoate with q.s is used as the reaction initiator as reaction solvent with a small amount of P-toluenesulphonic acids, can obtain to prepare the best effect of hydroxyl (thion) triazole.Suitable high temperature range is 80～120 ℃.But this preparation process also can be carried out in inert solvent, and as acid amides or sulfoxide solvent, this only need be with about stoichiometric manthanoate amount.Certainly, present method also can be used under the above temperature condition of solvent boiling point, by finish this synthesis step under pressure.
Hydroxyl (thion) triazole is converted into ethyl ester of the present invention (R in the formula
2: alkoxyl group), this conversion is to be by them and molecular formula
When needing other products of the present invention, be easy to be transformed with the ester of above-mentioned steps preparation.With such ester directly by itself and suitable replacement amine or to be converted into acid amides with the ammonium hydroxide reaction be possible.This speed of response is slower, but also can use if needed.Reaction can be in office what easily in the solvent, for example acid amides, ketone, sulfoxide are in room temperature or carry out under the suitable hot conditions below 100 ℃ greatly.
Ester is easy to be hydrolyzed to corresponding carboxylic acid.Hydrolytic reagent is an inorganic strong alkali extremely easily, for example basic metal hydride and carbonate, especially hydride.Aqueous alkanol such as methyl alcohol, ethanol etc. all can be used for hydrolysis easily and be optimal.Under the reflux temperature of reaction medium, carry out data, to prepare the acid of very economical high yield.
Carboxylic acid can be easy to be converted into any required salt, ester or acid amides of the present invention.Acid is with common method, for example by carrying out esterification with suitable ethanol.At first acid is converted into the acyl group fontanel, the method for conversion can be earlier by with reactions such as thionyl chloride, thionyl bromide, phosphorus base chlorine, then with ethanol synthesis, in general, this is very easily.In the presence of mineral acid, sulfuric acid particularly is perhaps under coupler participates in, as fmoc-2 imidazole.Finishing of esterification can be directly and ethanol synthesis, and the acyl group fontanel can be emanated, and maybe can be generated and further react in identical reaction mixture.Cheap inert solvent such as perfume compound etc. all are the suitable reaction solvents of the inventive method.In other words, acid can be with required R
2The halogenide of group is finished reaction in the presence of highly basic such as basic metal alkoxide, to obtain esterification.
At last, carboxylic acid is converted into corresponding amide by reacting with suitable replacement amine or with ammonium hydroxide.Preferentially adopt coupler, for example available phosphinylidyne diimidazole in such reactions steps, and preferentially adopt and in high inert solvent, implement method of the present invention as acid amides, in this class amide solvent, preferably use as dimethyl formamide and N,N-DIMETHYLACETAMIDE earlier.These are reflected at and are easy under reasonable time cycle and the room temperature condition carry out.
The salt of carboxylic acid is easy to prepare with general method, promptly by compound is simply contacted and can preparation obtain in moisture alkanol or moisture ketone with suitable alkali.For example, can obtain the basic metal salt by using as lithium hydroxide or potassium hydroxide, carbonate or supercarbonate.Amine salt is by obtaining with amine alkali such as triethylamine, triethanolamine, pyridine, butyl dimethylamine etc.Salt is prepared under 0～100 ℃ optimal temperature condition.
In addition, the present invention also provides the method for the compound of preparation molecule formula I
In the formula
X:-O-or-S-;
Ar: phenyl or by being selected from fontanel arbitrarily, trifluoromethyl, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, difluoro-methoxy, trifluoromethoxy, five fluorine oxyethyl groups and 1,1,2,1 or 2 group substituted-phenyls of 2-tetrafluoro oxyethyl group;
R
1: C
1-C
4Primary alkyl or secondary alkyl;
R
2: hydroxyl, C
1-C
4Alkoxyl group, benzyloxy, phenoxy group or-NR
4R
5;
R
3: hydrogen or C
1-C
4Primary alkyl or secondary alkyl;
R
4And R
5: hydrogen, C respectively do for oneself
3-C
6Cycloalkyl or C
1-C
3Alkyl or R
4And R
5Chemical combination also combines with nitrogen-atoms and to generate morpholino, tetramethyleneimine generation or piperidino-(1-position only); Or it can be the salt that plant is accepted, and comprising:
A. molecule formula II (Ar, R in the formula
3The same with the definition of X) compound act on mutually with the compound of molecule formula III
R in the formula III
1Definition the same, Y is a chlorine or bromine, Alk is C
1-C
4Alkyl, the compound of generation molecule formula I in the presence of highly basic, R in the formula
2Be C
1-C
4Alkoxyl group; Or
B. hydrolysis molecule formula I (R in the formula
2Be C
1-C
4Alkoxyl group) compound is to provide molecule formula I (R in the formula
2Be OH) compound; Or
C. molecule formula IV (Ar, R in the formula
1, R
3The same with the definition of X, R
6Be OH or Cl) compound and C
1-C
4Alcohol acts on mutually, so that molecule formula I (R in the formula to be provided
2Be C
1-C
4Alkoxyl group) compound,
D. molecule formula I (R in the formula
2Be OH or C
1-C
4Alkoxyl group) compound and ammonium hydroxide or molecular formula NHR
4R
5Amine (R in the formula
4And R
5Define the same) effect mutually, to produce molecule formula I (R in the formula
2Be NHR
4R
5) compound;
If needed, make the compound salify (R in the formula of molecule formula I
2Be OH) be the receptible salt of plant so that it to be provided.
Following preparation and embodiment further specify the synthetic of compound of the present invention.It will be understood that illustrated preparation method and embodiment, and be familiar with vitochemical people and can find thus that in order to prepare other compounds of the present invention most effectively, to some embodiment wherein, the condition of improving synthetic method is desirable.
Preparation method 1:1-(2, the 4-dichlorophenyl) the chloro urea
Adding 200 ml waters in the 20 gram 2,4 dichloro benzene base hydrazine hydrochlorides are with 80 ℃ of this solution heating.Then 6.8 gram potassium cyanates are dissolved in 75 ml waters, this solution is splashed into first solution.Mixing solutions stirs 4 hours postcooling under 80 ℃ of conditions.By filtration, drying, and, obtain the required intermediate of 11.8 grams with ethanol recrystallize collection product.
Preparation method 2:3-hydroxyl-1-phenyl-1,2, the 4-1H-triazole
100 gram 1-N-anilides base ureas add 500 milliliters of tri-methyl ortho formates, more about 400 milligrams of P-toluenesulphonic acidss are added this mixing solutions.The violent stirring heating is 2 hours in vapor bath, moves on to cooling and vacuum-evaporation in the big flask then.Residue carries out recrystallize with about 1600 milliliters of ethanol, obtains required 97 gram fusing points and be 277～280 ℃ intermediate.
Theoretical value: C 59.62; H 4.38; N 26.07;
Actual value: C 59.35; H 4.25; N 25.86.
Preparation method 3:3-hydroxy-5-methyl base-1-phenyl-1,2, the 4-1H-triazole
25 gram 1-N-anilides base urea and 150 milliliters of mutual chemical combination of trimethylammonium ortho ester add 100 milligrams of P-toluenesulphonic acidss, in vapor bath mixed solution are stirred 5 hours, then cooling and vacuum-evaporation.Residue carries out recrystallize with ethanol, obtains the required product of 24.6 grams.
Theoretical value: C 61.70; H 5.18; N 23.99;
Actual value: C 61.62; H 5.32; N 23.79.
Preparation method 4:1-(4-chloro-phenyl-) thiosemicarbazide
Add 250 milliliters of industrial alcohols in 50 gram 4-chloro-phenyl-hydrazine hydrochlorides and the 40 gram ammonium thiocyanates, mixed solution stirred 16 hours under the reflux condition.Static then guarantor's heat is filtered, with about 100 milliliters of hot ethanol washing leaching cakes.In filtrate when cooling,, product begins crystallization, collects product then, carries out recrystallize with industrial spirit again, obtains 32.7 gram fusing points and be 200～201 ℃ required intermediate.
Theoretical value: C 41.69; H 4.00; N 20.84;
Actual value: C 41.66; H 3.85; N 20.56.
Preparation method 5:1-(4-chloro-phenyl-)-and 3-thion-1,2, the 4-1H-triazole
12 gram 1-(4-chloro-phenyl-s) thiosemicarbazide is suspended in 60 milliliters 95% formic acid, mixed solution was stirred 24 hours under the condition of reflux.Cooling mixed liquid then, the product precipitation is collected product and with cold industrial spirit washing, and is dry then, obtains required intermediate 6.1 and restrains 222～224 ℃ of fusing points.
Theoretical value: C 45.39; H 2.86; N 19.85;
Actual value: C 45.41; H 2.60; N 19.62.
Above-mentioned preparation method illustrates first and second intermediates synthetic of all products of the present invention.Prepare any intermediate in order to obtain top efficiency, above-mentioned condition is only done slightly to adjust just can satisfy the demand.
Embodiment 1:3-(1-ethyl ester oxyethyl group)-and 1-phenyl-1,2, the 4-1H-triazole
5 compounds of restraining Preparation Method 2 are dissolved in 75 milliliters of methyl-sulphoxides, add 1.7 gram sodium methylates.Stirred solution is 1 hour in vapor bath, removes the methyl alcohol that has formed then simply under vacuum.Add 5.6 gram 2 bromopropionic acid ethyl esters, mixed solution stirs in vapor bath and spends the night.Pour into then in the frozen water, collect the solid that generates and carry out drying, use the methanol-water crystallization.Throw out is dissolved in a small amount of ether, washes with water again with the 1N aqueous NaOH earlier then, use dried over mgso.Solvent removed in vacuo obtains 600 milligrams of required products, and fusing point is 88～89 ℃.
Theoretical value: C 59.76; H 5.97; N 16.08;
Actual value: C 59.64; H 5.97; N 15.85.
Embodiment 2:3-(1-ethoxycarbonyl oxyethyl group)-and 1-(2, the 4-dichlorophenyl)-1,2, the 4-1H-triazole
With 13 gram 3-hydroxyl-1-(2,4-dichlorophenyl)-1,2, the 4-1H-triazole is added to sodium methylate (being produced by 1.3 gram sodium and the excessive methanol) solution of 200 milliliters of methyl-sulphoxides.Solution heated in vapor bath 2 hours, added 10 gram 2 bromopropionic acid ethyl esters then, continued heating more than 1.5 hours, and cooling mixed liquid is poured on the frozen water, with 200 milliliters of ether extraction.With 1N hydrochloric acid, moisture saturated sodium bicarbonate and saturated brine washing, use sodium sulfate and phase separation paper drying then successively.Solvent removed in vacuo obtains the required product of 16 grams, finish.
Theoretical value: C 47.29; H 3.97; N 12.73;
Actual value: C 47.09; H 4.06; N 12.48.
Embodiment 3:3-(1-ethoxycarbonyl oxyethyl group)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
1.7 gram sodium is dissolved in 30 ml methanol, and this solution is added in 150 milliliters of methyl-sulphoxides.Add 17 gram 3-hydroxyl-1-(3-trifluoromethyls again)-1,2, the 4-1H-triazole was placed in the vapor bath heating 90 minutes with solution.Add 13.4 gram 2 bromopropionic acid ethyl esters then, continue heating more than 90 minutes, collect solid, carry out drying, carry out recrystallize, obtain required product 20.5 grams, 100～102 ℃ of fusing points with ethanol.
Theoretical value: C 51.07; H 4.29; N 12.76;
Actual value: C 50.83; H 4.48; N 12.83.
Embodiment 4:1-(2-chloro-phenyl-)-and 3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
Method is basically according to the foregoing description 2, and initial usefulness 1.2 restrains sodium, 30 ml methanol, 10 gram 1-(2-chloro-phenyl-s)-3-hydroxyl-1,2,4-1H-triazole and 9.3 gram 2 bromopropionic acid ethyl esters.Solvent is 100 milliliters of methyl-sulphoxides.The product that obtains is the required products of 14 grams, finish.
Theoretical value: C 52.80; H 4.77; N 14.21;
Actual value: C 52.61; H 4.77; N 13.98.
Embodiment 5:1-(3-chloro-phenyl-)-and 3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
2.2 gram sodium is dissolved in 75 ml methanol, and this solution is added 100 milliliters of methyl-sulphoxides, adds 19.2 gram 1-(3-chloro-phenyl-s again)-3-hydroxyl-1,2, the 4-1H-triazole stirred this mixture 4 hours in vapor bath.And then add 17.7 gram 2 bromopropionic acid ethyl esters, and continuing heating more than 2 hours, cooling mixed liquid is poured on the frozen water, collects solid, drying, and carry out recrystallize with toluene again with ethanol earlier, and obtaining the required product of 8.5 grams, fusing point is 70～71 ℃.
Theoretical value: C 52.80; H 4.77; N 14.21;
Actual value: C 52.97; H 4.60; N 14.47.
Embodiment 6:1-(3, the 4-dichlorophenyl)-3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
Method is similar to embodiment 5 basically, with 0.8 gram sodium, 20 ml methanol, 100 milliliters of methyl-sulphoxides, 8 gram 1-(3,4-dichlorophenyl)-3-hydroxyl-1,2,4-1H-triazole and 6.3 gram 2 bromopropionic acid ethyl esters.Product is the required products of 7.7 grams, 69～71 ℃ of fusing points.
Theoretical value: C 47.29; H 3.97; N 12.73;
Actual value: C 47.13; H 3.87; N 12.54.
Embodiment 7:3-(1-ethoxycarbonyl oxyethyl group)-and 5-methyl isophthalic acid-phenyl-1,2, the 4-1H-triazole
3.2 gram sodium are dissolved in 50 ml methanol, then this solution are added in 100 milliliters of methyl-sulphoxides.Add 24.6 gram 3-hydroxy-5-methyl base-1-phenyl-1,2 again, the 4-1H-triazole heated this solution 2 hours in vapor bath, add 100 milliliters of methyl-sulphoxides again.Then 25.4 gram 2 bromopropionic acid ethyl esters are added this solution, heat continuously more than 2 hours.With the reaction mixture cooling, be poured on the frozen water, with 300 milliliters of chloroform extraction.Water and saturated brine washing extract are also used sodium sulfate and phase separation paper drying.Vacuum removes solvent and distills under 1.2 millimeters of mercury and 192 ℃ of conditions, obtains the required product of 20 grams, finish.
Theoretical value: C 61.08; H 6.22; N 15.26;
Actual value: C 61.37; H 6.34; N 15.39.
Embodiment 8:3-(1-ethoxycarbonyl oxyethyl group)-and the 1-(4-p-methoxy-phenyl)-1,2, the 4-1H-triazole
1.3 gram sodium is dissolved in 30 ml methanol, and this solution is added in 150 milliliters of methyl-sulphoxides.Add 11 gram 3-hydroxyl-1-(4-p-methoxy-phenyls again)-1,2, the 4-1H-triazole, this solution heated 2 hours under 60 ℃ of conditions.Add 10.4 gram 2 bromopropionic acid ethyl esters then, this mixed solution is heating more than 4 hours in the vapor bath.Be poured on after the cooling on the frozen water, collect solid, drying is used the alcohol-water recrystallize.Impure product was with 1: 1 ethyl acetate: (just) hexane purifying and by filling the high-performance liquid chromatography of silica gel.Removal contains the solvent in the product cut, obtains the required product of 6.3 grams, 62～64 ℃ of fusing points.
Theoretical value: C 57.72; H 5.88; N 14.42;
Actual value: C 57.43 H 5.69; N 14.70.
Embodiment 9:3-(1-ethoxycarbonyl butoxy)-and 1-phenyl-1,2, the 4-1H-triazole
Synthetic method is except need carrying out the stratographic analysis by 8 pairs of products of embodiment, and other are identical with the foregoing description 7 basically.Reagent is 0.7 gram sodium, 20 ml methanol, 5 gram 3-hydroxyl-1-phenyl-1,2,4-1H-triazole and 6.5 gram 2 bromopropionic acid ethyl esters.Solvent is 80 milliliters of methyl-sulphoxides.Obtain the required product of 5 grams, finish.
Theoretical value: C 62.27; H 6.62; N 14.52;
Actual value: C 62.04; H 6.90; N 14.25.
Embodiment 10:3-(1-ethoxycarbonyl pentyloxy)-and 1-phenyl-1,2, the 4-1H-triazole
Method such as above-mentioned embodiment 7, initial usefulness 1.4 gram sodium, 30 ml methanol, 150 milliliters of methyl-sulphoxides, 10 gram 3-hydroxyl-1-phenyl-1,2,4-1H-triazole and 13.8 gram 2 bromopropionic acid ethyl esters.Product distills under 205 ℃ and 1 millimeter of mercury condition, obtains the required product of 5.2 grams, finish.
Theoretical value: C 63.35; H 6.98; N 13.85;
Actual value: C 63.62; H 7.14; N 13.75.
Embodiment 11:3-(1-ethoxycarbonyl oxyethyl group)-and the 1-(4-tolyl)-1,2, the 4-1H-triazole
Method is as described in the embodiment 8, initial usefulness 1.1 gram sodium, 20 ml methanol, 150 milliliters of methyl-sulphoxides, 8.5 gram 3-hydroxyl-1-(4-tolyls)-1,2,4-1H-triazole and 8.7 gram 2 bromopropionic acid ethyl esters.Obtain required product 3.8 grams, 69～71 ℃ of fusing points
Theoretical value: C 61.08; H 6.22; N 15.27;
Actual value: C 60.90; H 6.22; N 15.11.
Embodiment 12:1-(4-chloro-phenyl-)-and 3-(1-ethyl ester oxyethyl group)-1,2, the 4-1H-triazole
With 6 gram 1-(4-chloro-phenyl-s)-3-hydroxyl-1,2, the 4-1H-triazole is added to and contains 1.5 and digest in 225 milliliters of methyl-sulphoxide suspension of sodium, and mixed solution heated in vapor bath 90 minutes.Add 5.5 gram 2 bromopropionic acid ethyl esters then, heat this mixed solution more than 90 minutes again.After cooling, be poured on the frozen water, collect solid, drying and use the toluene recrystallize, obtain the required product of 1.5 grams, 62～64 ℃ of fusing points
Theoretical value: C 52.80; H 4.77; N 14.21;
Actual value: C 52.89; H 4.89; N 14.08.
Embodiment 13:1-(4-chloro-phenyl-)-3-(1-ethoxycarbonyl oxyethyl group)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
Method is except carrying out purifying also with acetate-(just) hexane ethyl ester wash-out with silica gel column chromatography to product, and other are described identical with embodiment 4.Reactant is 0.5 gram, 15 ml methanol, 50 milliliters of methyl-sulphoxides, 4.9 gram 1-(4-chloro-phenyl-s)-3-hydroxy-5-methyl base-1,2,4-1H-triazole and 4.2 gram 2 bromopropionic acid ethyl esters.The yield of required product is 4.5 grams, finish.
Theoretical value: C 54.29; H 5.21; N 13.57;
Actual value: C 54.04; H 5.39; N 13.32.
Embodiment 14:3-(1-ethoxycarbonyl oxyethyl group)-and 1-(2, the 6-3,5-dimethylphenyl)-1,2, the 4-1H-triazole
Method is except the ethyl acetate of chromatographic column with 1: 1: (just) hexane wash-out, other are described identical with embodiment 13.Reactant is 0.8 gram sodium, 20 ml methanol, 50 milliliters of methyl-sulphoxides, 6.9 gram 3-hydroxyl-1-(2,6-xylyl)-1,2,4-1H-triazole and 6.6 gram 2 bromopropionic acid ethyl esters.The yield of required thing is 6 grams, finish.
Theoretical value: C 62.27; H 6.62; N 14.52;
Actual value: C 61.97; H 6.87; N 14.31.
Embodiment 15:3-(1-ethoxycarbonyl oxyethyl group)-and the 1-(3-aminomethyl phenyl)-1,2, the 4-1H-triazole
Method is that other are described identical with embodiment 7 basically with ether rather than with the chloroform extraction except first aqueous mixture, and reactant is 1.5 gram sodium, 20 ml methanol, 11.4 gram 3-hydroxyl-1-(3-aminomethyl phenyl)-1,2,4-1H-triazole and 11.8 gram 2 bromopropionic acid ethyl esters.The yield of required product is 12.9 grams, finish.
Theoretical value: C 61.08; H 6.22; N 15.26;
Actual value: C 60.83; H 6.09; N 15.08.
Embodiment 16:3-(1-ethoxycarbonyl propoxy-)-and 1-phenyl-1,2, the 4-1H-triazole
Method is not except aqueous mixture distills without chloroform extraction and product with ethyl acetate, and other are described identical with described embodiment 7 basically.Reactant is 0.7 gram, 20 ml methanol, 50 milliliters of methyl-sulphoxides, 5 gram 3-hydroxyl-1-phenyl-1,2,4-1H-triazole and 6 gram 2 bromopropionic acid ethyl esters.The yield of required product is 5.2 grams, finish.
Theoretical value: C 61.08; H 6.22; N 15.26;
Actual value: C 60.82; H 6.37; N 14.99.
Embodiment 17:1-(3-chloro-phenyl-)-3-(1-ethoxycarbonyl oxyethyl group)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
Method is described identical with the foregoing description 9, initial usefulness 0.8 gram sodium, 20 ml methanol, 75 milliliters of methyl-sulphoxides, 7.8 gram 1-(3-chloro-phenyl-s)-3-hydroxy-5-methyl base-1,2,4-1H-triazole and 6.7 gram 2 bromopropionic acid ethyl esters.Required efficiency of pcr product is 7.8 grams, finish.
Theoretical value: C 54.29; H 5.21; N 13.57;
Actual value: C 53.97; H 5.49; N 13.80.
Embodiment 18:3-(1-ethoxycarbonyl oxyethyl group)-and the 1-(2-aminomethyl phenyl)-1,2, the 4-1H-triazole
Method except aqueous mixture with the ethyl acetate extraction, other are described identical with the foregoing description 4.Method begins with 0.7 gram sodium, 15 ml methanol, 100 milliliters of methyl-sulphoxides, 5.4 gram 3-hydroxyl-1(2-aminomethyl phenyls)-1,2,4-1H-triazole and 5.6 gram 2 bromopropionic acid ethyl esters.The yield of required product is 5.0 grams, finish.
Theoretical value: C 61.08; H 6.22; N 15.26;
Actual value: C 61.34; H 5.97; N 15.03.
Embodiment 19:1-(4-bromophenyl)-and 3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
3.9 gram sodium are dissolved in being added to behind 50 milliliters of ethanol contain 41 gram 1-(4-bromophenyls)-3-hydroxyl-1,2, in the solution of 150 milliliters of methyl-sulphoxides of 4-1H-triazole.Mixture heated 45 minutes under 60 ℃ of conditions, added 30.9 gram 2 bromopropionic acid ethyl esters then.With mixture heating up postcooling more than 2 hours, be poured on the frozen water.Collect solid, drying is carried out recrystallize with toluene.Mother liquor carries out vacuum concentration, and residue carries out recrystallize with ethanol.This product and first product chemical combination also carry out recrystallize with ethanol, obtain required product 27.9 grams, 64～66 ℃ of fusing points
Theoretical value: C 45.90; H 4.15; N 12.35;
Actual value: C 45.77; H 3.96; N 12.39.
Embodiment 20:1-(3-bromophenyl)-and 3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
Method is described identical with embodiment 3, initial usefulness 2.8 gram sodium, 50 milliliters of ethanol, 75 milliliters of methyl-sulphoxides, 29 gram 1-(3-bromophenyls)-3-hydroxyl-1,2,4-1H-triazole and 21.9 gram 2 bromopropionic acid ethyl esters.The yield of required product is 31.8 grams, 83～85 ℃ of fusing points.
Theoretical value: C 45.90; H 4.15; N 12.35;
Actual value: C 46.11; H 3.91; N 12.32.
Embodiment 21:1-(3, the 4-dichlorophenyl)-3-(1-ethoxycarbonyl propoxy-)-1,2, the 4-1H-triazole
Method is identical with embodiment 4, initial usefulness 0.4 gram sodium, 20 ml methanol, 75 milliliters of methyl-sulphoxides, 4 gram 1-(3,4-dichlorophenyl)-3-hydroxyl-1,2,4-1H-triazole and 3.4 gram 2-bromo-butyric acid ethyl esters.The impure efficiency of pcr product that contains ethyl ester and methyl esters is 6 grams.Product does not give purifying, but by embodiment 33 described being hydrolyzed.
Embodiment 22:3-(1-carboxyl oxyethyl group)-and 1-phenyl-1,2, the 4-1H-triazole
Get compound 2.5 grams and the 2.2 gram potassium hydroxide of embodiment 1, be added in 50 milliliters of ethanol mixture reflux 3 hours.Pour frozen water then into, make mixture become acidity with concentrated hydrochloric acid.Collect solid and use alcohol crystal, obtain the required product of 0.9 gram, 140～142 ℃ of fusing points.
Theoretical value: C 56.65; H 4.75; N 18.02;
Actual value: C 56.32; H 4.36; N 17.91.
Embodiment 23:3-(1-carboxyl oxyethyl group)-and 1-(2, the 4-dichlorophenyl)-1,2, the 4-1H-triazole
Get the compounds of 7 gram embodiment 2 and 100 milliliters of ethanolic soln reflux 3 hours of 2.4 gram potassium hydroxide, carry out recrystallize, obtain required product 2.3 and restrain 151～153 ℃ of fusing points by embodiment 22 described collection products and with toluene.
Theoretical value: C 43.73; H 3.00; N 13.91;
Actual value: C 43.96; H 3.25; N 13.69.
Embodiment 24:3-(1-carboxyl oxyethyl group)-and 1-(3-trifluoromethyl-1,2, the 4-1H-triazole
Get the compounds of 15 gram embodiment 3 and 150 milliliters of ethanolic soln reflux 3 hours of 5.1 gram potassium hydroxide, carry out recrystallize, obtain required product 11.8 and restrain 206～208 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 47.85; H 3.35; N 13.95;
Actual value: C 47.93; H 3.52; N 13.92.
Embodiment 25:3-(1-carboxyl oxyethyl group)-and the 1-(3-chloro-phenyl-)-1,2, the 4-1H-triazole
Get the compounds of 6.7 gram embodiment 5 and 100 milliliters of ethanolic soln reflux 3 hours of 2.5 gram potassium hydroxide, carry out recrystallize, obtain required product 5.2 and restrain 197～199 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 49.36; H 3.77; N 15.70;
Actual value: C 49.42; H 3.69; N 15.60.
Embodiment 26:3-(1-carboxyl oxyethyl group)-and the 1-(2-chloro-phenyl-)-1,2, the 4-1H-triazole
Get the compounds of 10 gram embodiment 4 and 100 milliliters of ethanolic soln reflux 4 hours of 3.8 gram potassium hydroxide, by 22 described collection products among the embodiment and carry out recrystallize with ethanol thereafter with toluene earlier, obtain required product 3.1 and restrain 104～106 ℃ of fusing points.
Theoretical value: C 49.36; H 3.77; N 15.70;
Actual value: C 49.12; H 3.79; N 15.49.
Embodiment 27:3-(1-carboxyl oxyethyl group)-and the 1-(4-chloro-phenyl-)-1,2, the 4-1H-triazole
Get the compounds of 3 gram embodiment 12 and 100 milliliters of ethanolic soln reflux 2 hours of 1.1 gram potassium hydroxide, carry out recrystallize, obtain required product 1.9 and restrain 196～198 ℃ of fusing points by embodiment 22 described collection products and with ethyl acetate.
Theoretical value: C 49.36; H 3.77; N 15.70;
Actual value: C 49.17; H 3.97; N 15.46.
Embodiment 28:3-(1-carboxyl oxyethyl group)-and 1-(3, the 4-dichlorophenyl)-1,2, the 4-1H-triazole
Get the compounds of 4 gram embodiment 6 and 75 milliliters of ethanolic soln reflux 4 hours of 1.4 gram potassium hydroxide, carry out recrystallize, obtain required product 3.3 and restrain 222～224 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 43.73; H 3.00; N 13.91;
Actual value: C 44.01; H 3.01; N 13.83.
Embodiment 29:3-(1-carboxyl oxyethyl group)-and 5-methyl isophthalic acid-phenyl-1,2, the 4-1H-triazole
Get the compound of 10 gram embodiment 7 and 150 milliliters of alcohol refluxs of 4.1 gram potassium hydroxide and heated 4 hours, extract with the ethanol ethyl ester and collect product.Washing extract after drying is called vacuum-evaporation, and residue carries out recrystallize with toluene, obtains required product 2.1 grams, 157～159 ℃ of fusing points.
Theoretical value: C 58.29; H 5.30; N 16.99;
Actual value: C 58.13; H 5.32; N 16.85.
Embodiment 30:3-(1-carboxyl oxyethyl group)-and the 1-(4-p-methoxy-phenyl)-1,2, the 4-1H-triazole
Get the compounds of 4 gram embodiment 8 and 50 milliliters of ethanolic soln reflux 4 hours of 1.5 gram potassium hydroxide, carry out recrystallize, obtain required product 2.6 and restrain 155～157 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 54.75; H 4.98; N 15.96;
Actual value: C 54.51; H 5.15; N 15.75.
Embodiment 31:3-(1-carboxyl oxyethyl group)-and the 1-(2-aminomethyl phenyl)-1,2, the 4-1H-triazole
Get the compound of 3 gram embodiment 18 and 100 milliliters of ethanol of 1.2 gram potassium hydroxide, carry out recrystallize, obtain required product 2.3 grams, 151～153 ℃ of fusing points according to embodiment 22 described collection products and with ethanol.
Theoretical value: C 58.29; H 5.30; N 16.99;
Actual value: C 58.42; H 5.45; N 16.82.
Embodiment 32:3-(1-carboxyl oxyethyl group)-and the 1-(3-aminomethyl phenyl)-1,2, the 4-1H-triazole
Get the compound of 5 gram embodiment 15 and 50 milliliters of alcohol refluxs of 2 gram potassium hydroxide and heated 4 hours, carry out recrystallize, obtain required product 4.2 grams, 155～157 ℃ of fusing points according to embodiment 22 described collection products and with toluene.
Theoretical value: C 58.29; H 5.30; N 16.99;
Actual value: C 58.50; H 5.35; N 16.71.
Embodiment 33:3-(1-carboxyl propoxy-)-and 1-(3, the 4-dichlorophenyl)-1,2, the 4-1H-triazole
Get the products of 6 gram embodiment 21 and 100 milliliters of ethanolic soln reflux 2 hours of 2 gram potassium hydroxide, with this acidified reaction mixture of chloroform extraction, the washing extract is with sodium sulfate with roll over printing paper drying, vacuum-evaporation.Residue carries out recrystallize with ethanol, obtains required product 3.6 232～234 ℃ of fusing points of gram.
Theoretical value: C 45.50; H 3.51; N 13.29;
Actual value: C 45.85; H 3.74; N 13.08.
34:3-(1-carboxyl oxyethyl group among the embodiment)-and 1-(2, the 6-xylyl)-1,2, the 4-1H-triazole
Get the compound of 3 gram embodiment 14 and 100 milliliters of alcohol refluxs of 1.2 gram potassium hydroxide and heated 3 hours, press embodiment 22 described collection products, obtain required product 2.2 grams, 178～180 ℃ of fusing points.
Theoretical value: C 59.76; H 5.79; N 16.08;
Actual value: C 59.79; H 6.02; N 15.82.
Embodiment 35:3-(1-carboxyl oxyethyl group)-and the 1-(4-aminomethyl phenyl)-1,2, the 4-1H-triazole
Get the compounds of 2.5 gram embodiment 11 and 50 milliliters of ethanolic soln reflux 4 hours of 1 gram potassium hydroxide, press embodiment 22 described collection products, obtain required product 2.0 and restrain 163～165 ℃ of fusing points.
Theoretical value: C 58.29; H 5.30; N 16.99;
Actual value: C 58.06; H 5.03; N 16.79.
Embodiment 36:3-(1-carboxyl oxyethyl group)-the 1-(3-chloro-phenyl-)-the 5-methyl isophthalic acid, 2, the 4-1H-triazole
Get the compound of 3.8 gram embodiment 17 and 100 milliliters of alcohol refluxs of 1.4 gram potassium hydroxide and heated 4 hours, carry out recrystallize, obtain required product 2.8 grams, 101～103 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 51.17; H 4.29; N 14.92;
Actual value: C 51.35; H 4.49; N 14.84.
Embodiment 37:1-(4-bromophenyl)-and 3-(1-carboxyl oxyethyl group)-1,2, the 4-1H-triazole
Get the compounds of 10 gram embodiment 19 and 150 milliliters of alcoholic acid solution reflux 10 minutes of 3.3 gram potassium hydroxide, carry out recrystallize, obtain required product 8.0 and restrain 195～197 ℃ of fusing points by example 22 described collection products and with ethanol.
Theoretical value: C 42.33; H 3.23; N 13.46;
Actual value: C 42.23; H 3.35; N 13.36.
Embodiment 38:1-(3-bromophenyl)-and 3-(1-carboxyl oxyethyl group)-1,2, the 4-1H-triazole
Get the compounds of 28.8 gram embodiment 20 and 100 milliliters of ethanolic soln reflux 10 minutes of 9.5 gram potassium hydroxide, carry out recrystallize, obtain required product 21.6 and restrain 198～200 ℃ of fusing points by embodiment 22 described collection products and with ethanol.
Theoretical value: C 42.33; H 3.23; N 13.46;
Actual value: C 42.51; H 3.45; N 13.24.
Embodiment 39:1-(2, the 4-dichlorophenyl)-3-(1-methoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
Get the compound of 3 gram embodiment 23, be added in 75 milliliters of toluene and 5 milliliters of thionyl (two) chlorine, with this solution reflux 2 hours.Vacuum-evaporation is carried out in cooling then.50 milliliters of toluene are added to residue, and solvent removed in vacuo is added to 50 ml methanol with this residue again, and with this solution reflux 2 hours, the evaporation of cooling final vacuum.Residue toluene recrystallize obtains required product 0.68 gram, 74～75 ℃ of fusing points.
Theoretical value: C 45.59; H 3.51; N 13.29;
Actual value: C 45.70; H 3.34; N 13.37.
Embodiment 40:1-(2, the 4-dichlorophenyl)-3-(1-isopropyl ester base oxethyl)-1,2, the 4-1H-triazole
Get the compound of 3 gram embodiment 23, be added in 50 milliliters of toluene, add 5 milliliters of thionyl (two) chlorine again.With this mixture reflux 2 hours, the evaporation of cooling final vacuum.Add 50 milliliters of toluene final vacuums again and remove, then 50 milliliters of Virahols are added in the residue.This mixture reflux 2 hours, the evaporation of cooling final vacuum, residue carries out recrystallize with Virahol, obtains required product 2.6 grams, 55～57 ℃ of fusing points.
Theoretical value: C 48.85; H 4.39; N 12.21;
Actual value: C 48.60; H 4.35; N 12.00.
Embodiment 41:3-(1-benzyloxy oxyethyl group)-and 1-phenyl-1,2, the 4-1H-triazole
With 5.5 the gram embodiment 22 compounds be added to 50 milliliters contain 0.54 the gram sodium methyl alcohol in, then with this mixture reflux.The cooling final vacuum is removed solvent.Add 75 milliliters of toluene again, 2.6 milliliters of benzyl chlorides and 2.3 gram triethylamines were with this mixture reflux 22 hours.Be poured on after the cooling on the frozen water, use ethyl acetate extraction.Water and saturated brine are washed extract and are used sodium sulfate and phase separation paper drying.Vacuum-evaporation then, residue obtains required product 2.5 grams, 78～80 ℃ of fusing points with ethanol one water recrystallize.
Theoretical value: C 66.86; H 5.30; N 13.00;
Actual value: C 66.73; H 5.02; N 13.07.
Embodiment 42:3-(1-methoxycarbonyl oxyethyl group)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
The compound of getting 2.5 gram embodiment 24 is added in 50 milliliters of toluene, then 3 milliliters of thionyl (two) chlorine is added in this mixture reflux 2 hours, the evaporation of cooling final vacuum.50 milliliters of toluene are added to this residue and vacuum removal toluene, and this residue is placed methyl alcohol, reflux 3 hours.Vacuum is removed solvent, and with methyl alcohol residue is carried out recrystallize, obtains required product 2.0 grams, 135～137 ℃ of fusing points.
Theoretical value: C 49.53; H 3.84; N 13.33;
Actual value: C 49.25; H 3.64; N 13.36.
Embodiment 43:3-(1-isopropyl ester base oxethyl)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
According to embodiment 42 methods, but replace methyl alcohol with Virahol.Product carries out recrystallize with toluene, obtains required product 0.9 gram, 97～99 ℃ of fusing points.
Theoretical value: C 52.48; H 4.70; N 12.24;
Actual value: C 52.27; H 4.43; N 12.44.
Embodiment 44:3-(1-amino methyl base oxethyl)-and 1-phenyl-1,2, the 4-1H-triazole
The 2.5 gram compounds of embodiment 1 and 10 milliliter 40% are contained methylamine and 20 milliliters of dimethyl formamides chemical combination at ambient temperature, and mixture can leave standstill 2 days, poured in the frozen water then, collect solid matter, carry out dry air, obtain required product 0.4 gram, 134～135 ℃ of fusing points.
Theoretical value: C 58.53; H 5.73; N 22.75;
Actual value: C 58.51; H 5.82; N 22.54.
Embodiment 45:3-(1-dimethylamino methoxycarbonyl oxyethyl group)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
Restrain the compound dissolution of embodiment 24 in 20 milliliters of dimethyl formamides with 3, and add 3.4 the gram carboxyl diimidazoles, at room temperature stirred the mixture 20 minutes, the dimethylamine that adds 4 milliliter 40% then, and stirring at room one day are poured it in frozen water into, collect solid matter, drying only obtains required product 1.5 grams, 126～127 ℃ of fusing points again by ethanol.
Theoretical value: C 51.22; H 4.61; N 17.07;
Actual value: C 50.98; H 4.41; N 16.99.
Embodiment 46:3-(1-aminocarboxyl oxyethyl group)-and the 1-3-trifluoromethyl)-1,2, the 4-1H-triazole
Undertaken by embodiment 45 methods, initial with embodiment 24 compounds 5 grams, 4 gram carboxyl diimidazoles and 1.2 gram ammonium hydroxide.The yield of required product is 2.8 grams, 147～149 ℃ of fusing points.
Theoretical value: C 48.01; H 3.69; N 18.66;
Actual value: C 47.85; H 3.63; N 18.60.
Embodiment 47:1-(3-chloro-phenyl-)-and the amino dimethyl ester base oxethyl of 3-(1-)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 3 gram embodiment 25,2.7 gram carboxyl diimidazole and 3.6 milliliter of 40% moisture dimethylamine.Product carries out recrystallize with toluene, obtains required product 2.2 grams, 136～139 ℃ of fusing points.
Theoretical value: C 52.98; H 5.13; N 19.01;
Actual value: C 52.93; H 4.88; N 18.89.
Embodiment 48:1-(3-chloro-phenyl-)-and 3-(1-amino methyl base oxethyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, begins the compound with 3 gram embodiment 25,2.7 gram carboxyl diimidazoles, 3 milliliter of 40% moisture methylamine.Product carries out recrystallize with toluene, obtains required product 2.3 grams, 120～122 ℃ of fusing points.
Theoretical value: C 51.35; H 4.67; N 19.96;
Actual value: C 51.63; H 4.89; N 19.83.
Embodiment 49:1(3-chloro-phenyl-)-and 3-(1-aminocarboxyl oxyethyl group)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 2.8 gram embodiment 25,2.5 gram carboxyl diimidazole and 4 milliliters of ammonium hydroxide.Product obtains required product 1.3 grams, 143～145 ℃ of fusing points earlier with carrying out recrystallize with ethanol behind the toluene.
Theoretical value: C 49.54; H 4.16; N 21.01;
Actual value: C 49.72; H 3.96; N 21.20.
Embodiment 50:3-(1-amino methyl base oxethyl)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, initial usefulness 3 gram embodiment 24 compounds, 3.4 gram carboxyl diimidazole and 3 milliliter of 40% moisture methylamine.Product does not carry out recrystallize, obtains required product 2.7 grams, 137～139 ℃ of fusing points.
Theoretical value: C 49.96; H 4.17; N 17.83;
Actual value: C 49.84; H 3.94; N 17.82.
Embodiment 51:3-(1-B aminocarbonyl oxyethyl group)-and the 1-(3-trifluoromethyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 3 gram embodiment 24,3.4 gram carboxyl diimidazole and 2 milliliter of 70% aqueous ethylamine.Product ethanol recrystallize obtains required product 1.3 grams, 135～137 ℃ of fusing points.
Theoretical value: C 51.22; H 4.61; N 17.07;
Actual value: C 51.46; H 4.62; N 16.86.
Embodiment 52:3-(1-aminocarboxyl oxyethyl group)-and the 1-(4-bromophenyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 3 gram embodiment 37,2.6 gram carboxyl diimidazoles and 0.7 gram ammonium hydroxide.Product carries out recrystallize with ethanol, obtains required product 1.6 grams, 179～181 ℃ of fusing points.
Theoretical value: C 42.46; H 3.56; N 18.01;
Actual value: C 42.69; H 3.81; N 17.91.
Embodiment 53:1-(4-bromophenyl)-and 3-(1-amino methyl base oxethyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 3 gram embodiment 37,2.3 gram carboxyl diimidazole and 2 milliliter of 40% moisture methylamine.Product carries out recrystallize with ethanol, obtains required product 2.5 grams, 176～178 ℃ of fusing points.
Theoretical value: C 44.33; H 4.03; N 17.23;
Actual value: C 44.54; H 4.23; N 17.18.
Embodiment 54:3-(1-aminocarboxyl oxyethyl group)-and the 1-(3-bromophenyl)-1,2, the 4-1H-triazole
Method is identical with embodiment 45, the compound of initial usefulness 3 gram embodiment 38,2.3 gram carboxyl one imidazoles and 0.7 gram ammonium hydroxide.The yield of required product is 1.6 grams, non-recrystallization shape, 141～144 ℃ of fusing points.
Theoretical value: C 42.46; H 3.56; N 18.01;
Actual value: C 42.70; H 3.69; N 17.79.
The chloroformyl oxyethyl group of preparation method 6:3-(1-)-and 1-phenyl-1,2, the 4-1H-triazole
The 22.8 compound suspension that restrain embodiment 22 at 150 milliliters of toluene, are added 49 milliliters of thionyl (two) chlorine.With this mixture reflux 2 hours, the evaporation of cooling final vacuum.Add 100 milliliters of toluene and vacuum again and remove toluene.Residue carries out recrystallize with toluene.
Embodiment 55:3-(1-methoxycarbonyl oxyethyl group)-and 1-phenyl-1,2, the 4-1H-triazole
3 compounds of restraining agent (preparation method) 6 are added to 75 ml methanol, and with this solution reflux 1 hour.The cooling final vacuum is removed solvent.Residue is placed in 100 milliliters of ether, and water and saturated brine washing soln are with sodium sulfate and phase separation paper drying.Vacuum is removed ether, and residue carries out recrystallize with methyl alcohol, obtains required product 1.4 grams, 88～90 ℃ of fusing points.
Theoretical value: C 58.29; H 5.30; N 16.99;
Actual value: C 58.16; H 5.11; N 16.88.
Embodiment 56:3-(1-isopropoxy carbonyl oxyethyl group)-and 1-phenyl-1,2, the 4-1H-triazole
3 compounds of restraining agent 6 are added to 75 milliliters of Virahols and with this solution reflux 19 hours.The evaporation of cooling final vacuum, residue carries out recrystallize with toluene, obtains the required product of 1.1 grams, 104 ℃ of fusing points.
Theoretical value: C 61.08; H 6.22; N 15.26;
Actual value: C 60.90; H 5.98; N 15.19.
Embodiment 57:3-(1-ethoxy carbonyl oxyethyl group)-and the 1-(3-fluorophenyl)-1,2, the 4-1H-triazole
1.7 gram sodium are dissolved in 50 milliliters of dehydrated alcohols, and this solution are added to 13.3 gram 1-(3-fluorophenyls)-3-hydroxyl-1,2, in the solution of 150 milliliters of methyl-sulphoxides of 4-1H-triazole.This solution heated in vapor bath 15 minutes, added 13.5 gram 2 bromopropionic acid ethyl esters then, and this mixture heated in vapor bath 2 hours.It is poured on the frozen water, this aqueous mixture ether extraction, water and salt water washing organic layer are used sodium sulfate and phase separation paper drying then.Situation is removed solvent, and product carries out recrystallize with aqueous ethanol, obtains the required product of 6.7 grams, 35～37 ℃ of fusing points.
Theoretical value: C 55.91; H 5.05; N 15.05;
Actual value: C 55.68; H 5.03; N 14.82.
Embodiment 58:3-(1-hydroxyl-oxethyl)-the 1-(3-fluorophenyl)-1-1,2, the 4-1H-triazole
100 milliliters of ethanol chemical combination of the product of 4 gram embodiment 57 and the potassium hydroxide of 1.6 grams, the mixture reflux is poured on after the cooling on the frozen water, carries out acidifying with hydrochloric acid, collects product by filtering, and obtains 3.4 and restrains at first compound, 177～179 ℃ of fusing points.
Theoretical value: C 52.59; H 4.01; N 16.73;
Actual value: C 52.76; H 4.25; N 16.89.
Embodiment 59:3-(1-aminocarboxyl oxyethyl group)-and the 1-(3-fluorophenyl)-1,2, the 4-1H-triazole
The product of 2 gram embodiment 58 is dissolved in 10 milliliters of dimethyl formamides, and adds 1.9 gram carbonyl dimidazoles.Mixture stirs 35% ammonium hydroxide that adds 0.6 gram after 20 minutes at ambient temperature.This mixture stirs at ambient temperature after 20 hours and pours frozen water into.Filter and collect product, drying obtains the required product of 1.4 grams, 156～158 ℃ of fusing points.
Theoretical value: C 52.80; H 4.43; N 22.39;
Actual value: C 52.80; H 4.22; N 22.46.
Embodiment 60:1-(4-bromophenyl)-and 3-(1-ethoxy carbonyl oxyethyl group)-1,2, the 4-1H-triazole
41 gram 1-(4-bromophenyls)-and 3-hydroxyl-1,2, the 4-1H-triazole is dissolved in 150 milliliters of methyl-sulphoxides, adds the sodium that 3.9 grams are dissolved in 50 milliliters of dehydrated alcohols again.Stirred 45 minutes under 60 ℃ of conditions of this mixture, add 30.9 gram 2 bromopropionic acid ethyl esters again.This mixture stirs more than 2 hours under 60 ℃ of conditions, is poured on after the cooling on the frozen water, filters and collects product and carry out drying.Carry out recrystallize with toluene, the mother liquor vacuum concentration.Residue concentrates with ethanol, and all products carry out chemical combination and carry out recrystallize with ethanol, obtains the required product of 27.9 grams, 64～66 ℃ of fusing points.
Theoretical value: C 45.90; H 4.15; N 12.35;
Actual value: C 45.77; H 3.96; N 12.39.
Embodiment 61:1-(4-bromophenyl)-and 3-(1-carboxyl oxyethyl group)-1,2, the 4-1H-triazole
The product potassium hydroxide hydrolysis of 10 gram embodiment 60, method is described identical with embodiment 58.Obtain the required product of 8.0 grams, 195～197 ℃ of fusing points.
Theoretical value: C 42.33; H 3.23; N 13.46;
Actual value: C 42.23; H 3.35; N 13.36.
Embodiment 62:1-(4-bromophenyl)-and 3-(1-cyclopropylamino carbonyl oxyethyl group)-1,2, the 4-1H-triazole
Press the method for embodiment 59, product, 2.4 gram carbonyl dimidazoles and the 1.1 gram cyclopropylaminos of initial usefulness 3 gram embodiment 61 grams.Product carries out recrystallize with ethanol, obtains the required product of 2.6 grams, 170～172 ℃ of fusing points.
Theoretical value: C 47.88; H 4.31; N 15.95;
Actual value: C 47.69; H 4.05; N 16.19.
Embodiment 63:1-(4-bromophenyl)-and the 3-(1-third aminocarboxyl oxyethyl group)-1,2, the 4-1H-triazole
2.4 gram carbonyl dimidazoles are added to 3 grams are dissolved among the embodiment of 20 milliliters of dimethyl formamides 61 product, this mixture stirred 20 minutes at ambient temperature.Add 1.2 grams, third amino then, this mixture stirred 3 days at ambient temperature, and it is poured on the frozen water, filtered and collected product and carry out drying.Carry out recrystallize with ethanol, obtain the required product of 2.3 grams, 144～145 ℃ of fusing points.
Theoretical value: C 47.61; H 4.85; N 15.86;
Actual value: C 47.85; H 5.03; N 15.86.
Embodiment 64:1-(3-bromophenyl)-and 3-(1-ethoxy carbonyl oxyethyl group)-1,2, the 4-1H-triazole
2.8 gram sodium are dissolved in 50 milliliters of dehydrated alcohols and are added to the 29 gram 1-(3-bromophenyls that are dissolved in 75 milliliters of methyl-sulphoxides)-3-hydroxyl-1,2, the 4-1H-triazole.This solution heated in vapor bath 30 minutes, added 21.9 gram 2 bromopropionic acid ethyl esters again, and this mixture is heating more than 2 hours in the vapor bath, be poured on after the cooling on the frozen water, filter and collect product, carry out drying, carry out recrystallize with ethanol, obtain 31.8 gram required compounds, 83～85 ℃ of fusing points.
Theoretical value: C 45.90; H 4.15; N 12.35;
Actual value: C 46.11; H 3.91; N 12.32.
Embodiment 65:1-(3-bromophenyl)-and 3-(1-carboxyl oxyethyl group)-1,2, the 4-1H-triazole
As among the embodiment as described in 59, with product hydrolysis in the ethanol that contains 9.5 gram potassium hydroxide of 28.8 gram embodiment 64.Product carries out recrystallize with ethanol, obtains the required product of 21.6 grams, 198～200 ℃ of fusing points.
Theoretical value: C 42.33; H 3.23; N 13.46;
Actual value: C 42.51; H 3.45; N 13.24.
Implement the routine 66:1-(3-bromophenyl of grain)-3-(1-cyclopropylamino carbonyl oxyethyl group)-1,2, the 4-1H-triazole
The product of 3 gram embodiment 65 is dissolved in 20 milliliters of dimethyl formamides, adds 2.4 gram carbonyl diurethane miaows again.This solution stirs at ambient temperature and adds 1.1 gram cyclopropylaminos after 20 minutes, and mixture stirred more than 16 hours, was poured on the frozen water, collected product, carried out recrystallize with ethanol after drying, obtains the required product of 2.1 grams, 134～135 ℃ of fusing points.
Theoretical value: C 47.88; H 4.31; N 15.95;
Actual value: C 48.01; H 4.25; N 15.98.
Embodiment 67:1-(3-bromophenyl)-and the 3-(1-third aminocarboxyl oxyethyl group)-1,2, the 4-1H-triazole
The products and 1.2 of 3 gram embodiment 65 restrain third ammonia react, method basically with embodiment in 66 described identical.Obtain the required product of 2.4 grams, 111～113 ℃ of fusing points.
Theoretical value: C 47.61; H 4.85; N 15.86;
Actual value: C 47.42; H 4.58; N 15.67.
Embodiment 68:3-(1-ethoxy carbonyl oxyethyl group)-and the 1-(4-trifluoromethyl)-1,2, the 4-1H-triazole
0.54 gram sodium is dissolved in 15 milliliters of dehydrated alcohols, is added to then to contain 5.4 gram 3-hydroxyl-1-(4-trifluoromethyls)-1,2,50 milliliters of methyl-sulphoxides of 4-1H-triazole.Add 25 milliliters of methyl-sulphoxides again, this mixture was heated in vapor bath 15 minutes.Add 4.3 gram 2 bromopropionic acid ethyl esters then and continue heating 1 hour.Being poured on behind the cooling mixture on the frozen water, collecting product, use high speed liquid chromatography method purifying after drying, is to carry out wash-out at 1: 1 with (just) hexane and ethyl acetate ratio, will contain the mutual chemical combination of cut of product then, through vacuum-evaporation, obtains required product 3.5 and restrains.
Theoretical value: C 51.07; H 4.29; N 12.76;
Actual value: C 51.27; H 4.42; N 12.85.
Embodiment 69:3-(1-carboxyl oxyethyl group)-and the 1-(4-trifluoromethyl)-1,2, the 4-1H-triazole
17.1 the compound of the embodiment 68 of gram successive reaction preparation, with 5.8 gram potassium hydroxide hydrolysis, method is described identical with embodiment 58 basically, obtains the required product of 15.5 grams, 215～218 ℃ of fusing points.
Theoretical value: C 47.85; H 3.35; N 13.95;
Actual value: C 48.04; H 3.27; N 13.95.
Embodiment 70:3-(1-aminocarboxyl oxyethyl group)-and the 1-(4-trifluoromethyl)-1,2, the 4-1H-triazole
The product of 3 gram embodiment 69 and the reaction of 0.7 gram, 35% ammonium hydroxide, method is described identical with embodiment 62 basically, obtains the required product of 2 grams, 178～180 ℃ of fusing points.
Theoretical value: C 48.01; H 3.69; N 18.66;
Actual value: C 47.80; H 3.52; N 18.54.
Embodiment 71:3-(1-dimethylamino carbonyl oxyethyl group)-and the 1-(4-trifluoromethyl)-1,2, the 4-1H-triazole
The product of 3 gram embodiment 69 and 4 milliliter of 45% moisture dimethylamine reaction, method is described identical with embodiment 62 basically.Obtain the required product of 1.2 grams, 102～104 ℃ of fusing points.
Theoretical value: C 51.22; H 4.61; N 17.07;
Actual value: C 51.04; H 4.67; N 17.10.
Embodiment 72:3-(1-cyclopropylamino carbonyl oxyethyl group)-and the 1-(4-trifluoromethyl)-1,2, the 4-1H-triazole
The product of 3 gram embodiment 69 and 1.1 gram propylamine reactions, method is described identical with embodiment 62 basically.Obtain the required product of 2.6 grams, 175～177 ℃ of fusing points.
Theoretical value: C 52.94; H 4.44; N 16.46;
Actual value: C 52.73; H 4.26; N 16.60.
Embodiment 73:3-(1-amino-carbonyl oxyethyl group)-and the 1(4-trifluoromethyl)-1,2, the 4-1H-triazole
The product of 3 gram embodiment 69 and 21 milliliters of moisture methylamine reactions, method is identical with embodiment 62 basically.Obtain the required product of 2.3 grams, 157 °～158 ℃ of fusing points.
Theoretical value: C 49.69; H 4.17; N 17.83;
Actual value: C 49.64; H 4.23; N 18.04.
Embodiment 74:3-(1-ethoxycarbonyl ethylmercapto group)-and 1-phenyl-1,2, the 4-1H-triazole
With 3 gram 1-phenyl-3-thions-1,2, the 4-1H-triazole is suspended in 50 milliliters of ethanol, adds 30 milliliters of ethanolic solns of 0.8 gram sodium hydroxide again.With this mixture reflux 15 minutes, add 3 gram 2 bromopropionic acid ethyl esters, again with this mixture reflux 2 hours.Be poured on after the cooling on the frozen water, use ethyl acetate extraction.Organic layer water, 2N aqueous NaOH and salt water washing, and with sodium sulfate and phase separation paper drying, vacuum is removed solvent, residue are as solvent by high speed liquid chromatography method to carry out purifying at 1: 1 with (just) hexane and ethyl acetate ratio.The mutual chemical combination of cut that will contain product through vacuum-evaporation, obtains the required product of 1.8 grams.
Theoretical value: C 56.30; H 5.45; N 15.15;
Actual value: C 56.60; H 5.23; N 15.34.
Embodiment 75:1-(3, the 4-dichlorophenyl)-3-(1-ethoxycarbonyl ethylmercapto group)-1,2, the 4-1H-triazole
With 11.5 gram 1-(3,4-dichlorophenyl)-3-thion-1,2, the 4-1H-triazole is dissolved in 100 milliliters in methyl-sulphoxide, is added to 1.1 gram sodium and is dissolved in 50 milliliters of dehydrated alcohols.This mixture was heated 1 hour under 60～80 ℃ of conditions, add 8.5 gram 2 bromopropionic acid ethyl esters, then this mixture was heated 2 hours under 100～110 ℃ of conditions, be poured on after the cooling on the frozen water, the aqueous mixture dichloromethane extraction is with salt water washing organic layer, dry on sal epsom, vacuum is removed solvent, and residue is with 2: 1 (just) hexane and eluent ethyl acetate, chromatography purification.Contain the mutual chemical combination final vacuum evaporation of cut of product, obtain the required product of 11 grams.
Theoretical value: C 45.10; H 3.78; N 12.14;
Actual value: C 44.91; H 3.72; N 11.87.
Embodiment 76:3-(1-ethoxycarbonyl oxyethyl group)-and 1-(4-trifluoromethoxy benzaldehyde base)-1,2, the 4-1H-triazole
With 11 gram 3-hydroxyl-1-(4-trifluoromethoxy benzaldehyde bases)-1,2, the 4-1H-triazole is dissolved in 100 milliliters of methyl-sulphoxides, adds 1.2 gram sodium and 20 milliliters of alcohol sodium solutions that dehydrated alcohol is made into, and adds 100 milliliters of methyl-sulphoxides again.This solution was heated in vapor bath 90 minutes, add 8.3 gram 2 bromopropionic acid ethyl esters then, continue heating more than 90 minutes.Be poured on the frozen water after the solution cooling, collect solid, carry out drying, obtain the required product of 15 grams, 52～53 ℃ of fusing points.
Theoretical value: C 48.70; H 4.09; N 12.17;
Actual value: C 48.93; H 4.21; N 12.34.
Embodiment 77:3-(1-carboxyl oxyethyl group)-and 1-(4-trifluoromethoxy benzaldehyde base)-1,2, the 4-1H-triazole
The compound of 13 gram embodiment 76 is removed ester by the method for embodiment 22, and product is separated and purifying, obtain required product 6.8 grams, 200～203 ℃ of fusing points by method among this embodiment.
Theoretical value: C 45.44; H 3.18; N 13.25;
Actual value: C 45.20; H 3.16; N 13.08.
Embodiment 78:1-(3, the 5-dichlorophenyl)-3-(1-ethoxycarbonyl oxyethyl group)-1,2, the 4-1H-triazole
1.8 gram sodium are dissolved in 75 milliliters of dehydrated alcohols and stirred solution are added to 18.5 gram 1-(3,5-dichlorophenyl lentamente)-3-hydroxyl-1,2, in 200 milliliters of dimethyl sulfoxide solutions of 4-1H-triazole.Stirred solution is 1 hour under 60 ℃ of conditions, adds 2 bromopropionic acid ethyl ester 14.5 grams then, under 100～110 ℃ of conditions this mixture heating up is poured on the frozen water after 2 hours, collects solid, carries out drying, uses the ether recrystallize, obtains the required product of 10 grams.Mother liquor is carried out chromatography, product 1.3 grams of getting back.
Theoretical value: C 47.29; H 3.97; N 12.73;
Actual value: C 47.07; H 4.03; N 12.57.
Embodiment 79:3-(1-carboxyl oxyethyl group)-and 1-(3, the 5-dichlorophenyl)-1,2, the 4-1H-triazole
The product of 11.3 gram embodiment 78 is removed ester by the method for embodiment 22, carry out recrystallize, obtain the required product of 10.5 grams, 230～231 ℃ of fusing points with ethanol/dichloromethane.
Theoretical value: C 43.73; H 3.00; N 13.91;
Actual value: C 44.08; H 3.24; N 13.63.
Compound of the present invention has multiple regulating action to the habit of many Plants, and perhaps the most important functions of these compounds is that they can slow down the growth of plant and reduce the strain shape of plant. Therefore, the space of processed plant is very little, can dense planting, and strain shape is short strong, thereby is unlikely lodged by wind and rain. In general, also will reduce needs to nutrition than plantlet.
Compound particularly to monocotyledons such as herbage, wheat, rice, cereals, also has effect to the plant organ of product pollen and seed, and also is like this to the effect of the dicotyledons such as cotton. Therefore, when a compound of the present invention was applied to turf, the formation on seed top and the growth of green grass all were suppressed, and the outer shape of turf is greatly improved therefrom. In addition, economically significance is the gamete effect of killing of compound. When compound is applied to plant, will suppress or prevent the generation of plant pollen. Therefore, aspect plant hybridization, the pollination plant can be easy to as maternal. Example is that at aspects such as generation hybridization cereal, wheat, rice, compound is conducive to as Cametocidal.
In addition, compound can increase sending out branch, bloom and bearing pods of various crops, particularly legume crop. The result is that the output of every plant all surpasses the plant without outer reason. Owing to use the compound of the present invention can dense planting, thereby improved the possibility of high yield benefit.
Furthermore, compound also has other facilitating effects. According to consumption, the service time of relevant floristics, compound and may also have other factors, panel length is shortened in its effect in addition, increase the quantity of the joint of joint number, increase growth leaf, branch or flower, improve the form of plant or each blade, or improving the root system of the plant of structure and the treated mistake of expansion, these effects of enumerating all are that compound of the present invention can provide.
Soybean is to use the especially desirable plant of The compounds of this invention. Other beans, clover, cotton and peanut that some desirable plants comprise soybean and plant for human consumer need. Other desirable plants comprise sod grass, cereal, wheat, barley, rice, rye and oat. Also have some desirable plants to comprise fruit tree, ornamental trees and nut trees. Some use compound of the present invention more preferably plant comprise soybean, sugar beet, cotton and cereal.
The time and the method that The compounds of this invention are used for plant can be had nothing in common with each other. Before the plant reproductive phase begins or close on when beginning like being the best time for use, therefore until plant grows the after date phase, compound of the present invention all can effectively use.
When plant closes on processing during the phase, the soil that compound is directly used in plant or the long root of plant is then ideal. It is best that this compound is directly used in plant with lobate spray pattern. For this reason, Traditionally the compound of agriculturally useful is mixed with the component of aqueous dispersion, and to use such component be best for practical application of the present invention.
In quite short interval, twice or repeatedly use this compound then more effective. Although the plant in the field is all once planted, they can in the same period not grown yet. Therefore, be the service time that suits to the plant that grows early, then may be too late for growing early plant. Use twice at couple of days or in some days, even three, four compounds, will improve the usefulness of this compound, thereby also can improve in some cases the proterties of processed crop.
Chemical compound lot remains effective in the extremely low situation of use amount. Desirable use amount is about 0.015～0.5 pound/acre. Another desirable use amount particularly is about 0.06～0.25 pound/acre to the soybean use amount. About 0.03～0.25 pound/acre then is another desirable amount ranges. The especially active very low compound of another desirable amount ranges then is about 0.25～2 pound/acre. Therefore, approximately the use amount from 0.015～5 pound/acre wide region then is special example, especially is reduced at utmost or another regulating action reaches to greatest extent plant, just can require such amount ranges.
The recipe ingredient of The compounds of this invention is pith of the present invention. These components comprise compound of the present invention and the diluent that can be accepted by plant. Most economical again optimal component is condensed water dispersed component or condensed water soluble component. Such component generally includes emulsible concentrate, suspensible concentrate, wettable pulvis and granular water-dispersible agent, these all are the components of generally using in the agriculture chemistry water jar territory. The reader understands so some discussion that they are done is be sure of to can be.
With regard to concentrating component, the use wide of the mark of the concentration of compound and compound. Re-use after these group farmings are diluted in water, and the consumption of compound is to be released than or determined by the amounts of components of the unit are of ploughing by component and water. Therefore, by obtaining any required consumption in any concentrated component. Peasant and agriculture chemistry worker are very familiar to required simple computation.
The emulsible concentration of compound comprises the suitable concentration that is dissolved in the compound in the diluent that plant can accept, and this diluent is the organic solvent that do not mix with water and the mixture of emulsifying agent. Usually available organic solvent comprises aromatic, and especially dimethylbenzene, and petroleum distillate is outstanding It is naphthalene and alkene two parts in the oil, and these are belonged to compound by the calculation aromatic series naphthalene of attaching most importance to. Comprise that the terpene solvent of rosin derivative and the mixed ethanol of cellosolvo one class also all are often to use, may be particularly useful to compound of the present invention as the acid amides of dimethylacetylamide one class. But the common amount ranges of emulsifying agent that is suitable for that emulsification concentrates is about 1%～10%(concentrate percentage by weight), slaine and amine salt that the ethylene oxide adduct, particularly alkylsurfuric acid of alkyl phenol in alkyl sulfate, the non-ionic surface active agent are arranged in the alkylbenzenesulfonate that often uses.
The wettability pulvis comprises the immixture of this compound and can replenish the diluent that can be accepted by plant of inert carrier and surfactant. Inert carrier usually is selected from the flour that is easy to aqueous dispersion, is a kind of active soil (attapulgite Clay), imvite, diatomite and the pure silicon hydrochlorate of the U.S.. The surfactant that is used for wettable pulvis finds from above-mentioned usefulness one type of emulsifiable concentrate that is applicable to, also has lignosulfonate and naphthalene sulfonate. Might be pressed into graininess to wettable pulvis, generate therefrom wettable particle, its advantage is no dust, is easy to measure and topple over. When adding entry, the wettable grain products of strict preparation will be dispersed in water, and become microparticle suspending liquid.
The compounds of this invention also can be mixed with suspension, contains higher concentration, considers The compounds of this invention is made fine powdery for economic interests, disperses and is suspended in the receptible diluent water of plant. The surfactant system that is used for product suspension to used very similar of wettable pulvis, but compound is kept for a long time in dispersed, in order to help the very intensive particle of compound can keep suspending, sometimes by indifferent salt is dissolved in liquid, with the density of suitable adjustment liquid.
When by through diluting when concentrating compound aqueous dispersion that component is prepared into and being used for blade, usual auxiliaries improves the ability of disperseing, with moistening and adhesion blade. This assistant commonly used has natural plant gum, emulsification polybutene, anion and other surfactants and lignin derivative. It is ideal using assistant in the aqueous dispersion of The compounds of this invention, and can constantly improve effect. Not only will effectively use the known commodity assistant of the person of cultivating, but also will effectively use common surfactant, the concentration of use is that percent zero point in dispersion is several.
The aqueous dispersion that concentrates component both can be used for blade, also can be used in the soil of plant growth. When being used for soil, it also is effective using grain fraction. Grain fraction on the agricultural comprises compound with common low concentration 0.1%～10%(percentage by weight according to appointment) be used for particulate vector with suitable particle size. In general, the size of particle is 20～60 orders (beaux yeux sieve mesh standards). All be often to use as carriers such as clay, sand, stone flour, corn cob grits, and for convenience and economy can select. Usually except compound and carrier, need not to use any assistant and other components, perhaps will with a small amount of solvent, make compound can be used for carrier. Carrier also can Powderedly provide and mix with powdered compounds with dust carrier, then this mixture is pressed into required particle size.
Provide below the embodiment of The compounds of this invention component, believe that the agriculture chemistry worker can manage the method that can prepare compound.
The suspension of embodiment 1
The compound 12.5% of embodiment 1
Tergitol TMN-6(non-ionic surface active agent) 10.0
Pure silicon stone 1.0
Polyfor H(lignosulphonates) 0.5
2% Xanthqn glue 10.0
Silicone antifoaming agent 0.2
Water 65.8
This compound and silica, Polyfon and part water is placed on is ground to 50% particle in the grater less than 2,3 microns, the suspension with development mixes with the residue of component then.
The wettable pulvis of embodiment 22
The compound 52.1% of embodiment 22
Palyfon O(lignosulphonates) 5.0%
Pure silicon stone 5.0%
Lauryl sodium sulfate 5.0%
Kaolin 32.9%
With each component mixing and through twice grinding of air impact grinder, make 50% particle less than 4.2 microns.
The compound 12.5% of embodiment 22
Pure silicon stone 1.0
Palyfon H 0.5
Silicone antifoaming agent 0.2
Tergitol TMN-6 10.0
2% Xanthan glue 10.0
Water 65.8
Compound and Tergitol, antifoaming agent, silica, Palyfon and part water place grater to be ground to 50% particle less than 2 microns, and the residue with Xanthen and water mixes then.
The suspension of embodiment 5
The compound 12.5% of embodiment 5
Silicone antifoaming agent 0.2
Pure silicon stone 1.0
2%Xanthan glue 10.0
Non-ionic surface active agent 10.0
Water 66.3
The processing of product is routine suspension as above.
The emulsifiable concentrate of embodiment 1
The compound 6.2% of embodiment
Propyl glycol methyl ether 20.0
Heavy aromatics naphtha 70.6
Toximul H(anion surfactant) 1.6
Toximul D(anion surfactant) 1.6
The suspension of embodiment 3
The compound 12.5% of embodiment 3
The used inert component 87.5 of the suspension of embodiment 5
The processing of product is identical with the suspension of embodiment 5, and the particle size of grinding is that 50% particle is less than 2.2 microns.
The suspension of embodiment 6
The compound 12.5% of embodiment 6
The inert component 87.5 that the suspension of embodiment 5 is used
The suspension of product such as embodiment 5 is processed, and the particle size of grinding is that 50% particle is less than 1.9 microns.
The emulsifiable concentrate of embodiment 1
The compound 6.2% of embodiment 1
Propyl glycol methyl ether 20.0
Heavy aromatics naphtha 68.0
Toximul H 2.9
Toximul D 2.9
Errata
Errata
Claims (8)
1, a kind of method for preparing molecular formula (I) compound
In the formula:
X:-O-or-S-;
Ar: phenyl or be selected from halogen, trifluoromethyl, C arbitrarily by 1 or 2
1-C
3Alkyl C
1-C
3Alkoxyl group, difluoro-methoxy, trifluoromethoxy, five fluorine oxyethyl groups and 1,1,2, the group substituted-phenyl of 2-tetrafluoro oxyethyl group;
R
1: C
1-C
4Primary alkyl or secondary alkyl:
R
2: hydroxyl, C
1-C
4Alkoxyl group, benzyloxy, phenoxy group or-NR
4R
5
R
3: hydrogen or C
1-C
4Primary alkyl or secondary alkyl:
R
4And R
5: hydrogen, C arbitrarily
3-C
6Cycloalkyl or C
1-C
3Alkyl or R
4And R
5Mutual chemical combination and combine with nitrogen-atoms and to generate morpholino, tetramethyleneimine generation or piperidino-(1-position only); Or its salt that can be accepted by plant, it comprises:
A. the compound of the compound of molecule formula II and molecule formula III reacts to each other in the presence of strong alkali
Ar, R in the formula
3It is the same with the definition of X,
R in the formula
1Definition the same, Y is a chlorine or bromine, AIK is C
1-C
4Alkyl, the compound of generation molecular formula (I), R in the formula
2Be C
1-C
4Alkoxyl group; Or
B. hydrolysis molecular formula (I) compound, R in the formula
2Be C
1-C
4Alkoxyl group is to provide the compound of molecular formula (I), R in the formula
2Be OH; Or
C. the compound of molecule formula IV, Ar, R in the formula
1, R
3The same with the definition of X, R
6Be OH or Cl, with C
1-C
4The alcohol reaction is to provide the compound of molecular formula (I), R in the formula
2Be C
1-C
4Alkoxyl group
D. the compound of molecular formula (I), R in the formula
2Be OH or C
1-C
4Alkoxyl group is with ammonium hydroxide or molecular formula NHR
4R
5Amine reaction, R in the formula
4And R
5Definition the same, to produce the compound of molecular formula (I), R in the formula
2Be NR
4R
5With
As needs, make the compound salify of molecular formula (I), R in the formula
2Be OH, with the salt that provides it to be accepted by plant.
2, according to the described method of claim 1, wherein (X is O to the compound of molecule formula II in the formula, R
3Be H) with the compound (R in the formula of molecule formula III
1Be methyl) reaction, (X is O in the formula, R with the compound that produces the molecule formula I
1Be methyl, R
2Be C
1-C
4Alkoxyl group, R
3Be H).
3, according to the described method of claim 1, wherein (X is O to the compound of molecule formula II in the formula, R
3Be H, Ar is 3-trichlorophenyl, 4-chloro-phenyl-or 3, and the 4-dichlorophenyl is with the compound (R in the formula of molecule formula III
1Be methyl) reaction, (X is O in the formula, and Ar is 3-chloro-phenyl-, 4-chloro-phenyl-, or 3,4-dichlorophenyl, R with compound that the molecule formula I is provided
1Be methyl, R
2Be C
1-C
4Alkoxyl group, R
3Be H).
4, according to the described method of claim 1, wherein (X is O to the compound of molecule formula I in the formula, R
1Be methyl, R
2Be C
1-C
4Alkoxyl group, R
3Be H, Ar is 3-chloro-phenyl-, 4-chloro-phenyl-, or 3, the 4-dichlorophenyl) be hydrolyzed, the compound of molecule formula I is provided, and (X is O in the formula, R
1Be methyl, R
2Be OH, R
3Be H, Ar is 3-chloro-phenyl-, 4-chloro-phenyl-, or 3, the 4-dichlorophenyl).
5, a kind of method of coordinate plant growth comprises the significant quantity as the compound of the defined molecule formula I of claim 1 is imposed on earlier than the plant of reproductive growth during the later stage.
6, according to the described method of claim 5, wherein the compound of molecule formula I is that X is O, R
1Be methyl, R
2Be OH or C
1-C
4Alkoxyl group, R
3Be H, Ar is 3-chloro-phenyl-, 4-chloro-phenyl-or 3,4-dichlorophenyl, or its salt that can be accepted by plant.
7, a kind of agricultural is used component, comprises combining as the compound of the defined molecule formula I of claim 1 and the thinner that can be accepted by plant.
8, component according to claim 7, wherein the compound of molecule formula I is that X is O, R
1Be methyl, R
2Be OH or C
1-C
4Alkoxyl group, R
3Be H, Ar is 3-chloro-phenyl-, 4-chloro-phenyl-or 3,4-dichlorophenyl, or its salt that can be accepted by plant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79730485A | 1985-11-12 | 1985-11-12 | |
| US797304 | 1985-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86107795A true CN86107795A (en) | 1987-06-03 |
Family
ID=25170457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686107795A Pending CN86107795A (en) | 1985-11-12 | 1986-11-10 | The triazole compounds of coordinate plant growth |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0227284A1 (en) |
| JP (1) | JPS62114973A (en) |
| KR (1) | KR900001162B1 (en) |
| CN (1) | CN86107795A (en) |
| AR (1) | AR243170A1 (en) |
| AU (1) | AU588646B2 (en) |
| BR (1) | BR8605573A (en) |
| CA (1) | CA1264744A (en) |
| DK (1) | DK538486A (en) |
| HU (1) | HUT43938A (en) |
| IL (1) | IL80601A0 (en) |
| NZ (1) | NZ218252A (en) |
| PH (1) | PH23227A (en) |
| PT (1) | PT83711B (en) |
| ZA (1) | ZA868551B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334084C (en) * | 2005-04-26 | 2007-08-29 | 武汉大学 | Bi-triazole compound, preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150245614A1 (en) * | 2012-09-06 | 2015-09-03 | Nippon Soda Co., Ltd. | Plant growth accelerator |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1943915C3 (en) * | 1968-09-04 | 1975-02-13 | Rohm And Haas Co., Philadelphia, Pa. (V.St.A.) | Substituted 3-mercapto-1,2,4triazoles and their use |
| US4318731A (en) * | 1979-08-25 | 1982-03-09 | Nihon Nohyaku Co., Ltd. | Δ2 -1,2,4-triazolin-5-one derivatives and herbicidal usage thereof |
| HU193891B (en) * | 1984-02-07 | 1987-12-28 | Gyogyszerkutato Intezet | Process for production of new derivatives of 1,2,4-triasole |
| FI850995L (en) * | 1984-03-16 | 1985-09-17 | Ciba Geigy Ag | FOERFARANDE FOER FRAMSTAELLNING AV NYA 3-MERKAPTO-1,2,4-TRIAZACYKLOALKADIENDERIVAT. |
-
1986
- 1986-11-10 CN CN198686107795A patent/CN86107795A/en active Pending
- 1986-11-10 CA CA000522602A patent/CA1264744A/en not_active Expired - Lifetime
- 1986-11-10 AR AR86305841A patent/AR243170A1/en active
- 1986-11-10 PT PT83711A patent/PT83711B/en unknown
- 1986-11-11 BR BR8605573A patent/BR8605573A/en unknown
- 1986-11-11 PH PH34461A patent/PH23227A/en unknown
- 1986-11-11 HU HU864657A patent/HUT43938A/en unknown
- 1986-11-11 DK DK538486A patent/DK538486A/en not_active Application Discontinuation
- 1986-11-11 ZA ZA868551A patent/ZA868551B/en unknown
- 1986-11-11 NZ NZ218252A patent/NZ218252A/en unknown
- 1986-11-11 EP EP86308759A patent/EP0227284A1/en not_active Ceased
- 1986-11-12 IL IL80601A patent/IL80601A0/en unknown
- 1986-11-12 AU AU65088/86A patent/AU588646B2/en not_active Ceased
- 1986-11-12 JP JP61269518A patent/JPS62114973A/en active Pending
- 1986-11-12 KR KR1019860009566A patent/KR900001162B1/en active IP Right Grant
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334084C (en) * | 2005-04-26 | 2007-08-29 | 武汉大学 | Bi-triazole compound, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ218252A (en) | 1988-07-28 |
| KR870004969A (en) | 1987-06-02 |
| PT83711B (en) | 1988-12-06 |
| KR900001162B1 (en) | 1990-02-27 |
| AR243170A1 (en) | 1993-07-30 |
| IL80601A0 (en) | 1987-02-27 |
| BR8605573A (en) | 1987-08-18 |
| EP0227284A1 (en) | 1987-07-01 |
| PT83711A (en) | 1986-12-01 |
| HUT43938A (en) | 1988-01-28 |
| PH23227A (en) | 1989-06-06 |
| AU588646B2 (en) | 1989-09-21 |
| CA1264744A (en) | 1990-01-23 |
| DK538486A (en) | 1987-05-13 |
| DK538486D0 (en) | 1986-11-11 |
| AU6508886A (en) | 1987-05-14 |
| JPS62114973A (en) | 1987-05-26 |
| ZA868551B (en) | 1988-01-27 |
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